Robert A. Shick

Functionalized polynorbornene dielectric polymers: Adhesion and mechanical properties

Within the microelectronics industry, there is an ongoing trend toward miniaturization coupled with higher performance. High glass-transition temperature polynorbornenes exhibit many of the key performance criteria necessary for these demanding applications. However, homopolynorbornene exhibits poor adhesion to common substrate materials, including silicon, silicon dioxide, aluminum, gold, and copper. In addition, this homopolymer is extremely brittle, yielding less than 1% elongation-to-break values. To address these issues, the homopolymer was functionalized to improve adhesive and mechanical properties. Attaching triethoxysilyl groups to the polymer backbone substantially improved the adhesion, but at the cost of increasing the dielectric constant because of the polarity of the functional group. Alkyl groups were also added to the backbone, which decreased the rigidity of the system, and resulted in significantly higher elongation-to-break values and a decrease in residual stress. The addition of an alkyl group slightly decreased the dielectric constant of the polymer as a result of an increase in molar volume. The coefficient of thermal expansion and modulus are also reported for the polynorbornene functionalized with triethoxysilyl groups using a multiple substrate approach.

Low k, Porous Methyl Silsesquioxane and Spin-On-Glass

Low dielectric constant, porous silica was made from commercially available methyl silsesquioxane (MSQ) by the addition of a sacrificial polymer, substituted norbornene polymer containing triethoxysilyl groups (NB), to the MSQ. The silsesquioxane-NB polymer film mixture was thermally cured followed by decomposition of the NB at temperatures above 400°C. The dielectric constant of the MSQ was lowered from 2.7 to 2.3 by creating 70 nm pores in the MSQ. The voids created in the MSQ exhibited a closed-pore structure. The concentration of NB in the MSQ affected the number of pores but not their size. Porous films were also created in a methyl siloxane spin-on-glass and its dielectric constant was lowered from 3.1 to 2.7. Infrared spectroscopy was used to follow the curing of the MSQ and decomposition of the NB.

Air-gaps in 0.3 μm electrical interconnections

A copper/air-gap interconnection structure using a sacrificial polymer and SiO/sub 2/ in a damascene process has been demonstrated. The air-gap occupies the entire intralevel volume with fully densified SiO/sub 2/ as the planar interlevel dielectric. The copper was deposited by physical vapor deposition and planarized by chemical-mechanical planarization. The Ta/Cu barrier/seed layer was deposited by physical vapor deposition; the bulk copper was electrochemically deposited. The resulting structure has an effective intralevel dielectric constant of 2.19.

Air‐Gaps for Electrical Interconnections

The fabrication of air-gap structures for electrical interconnections has been demonstrated using a sacrificial polymer encapsulated in conventional dielectric materials. The air-gap is formed by thermally decomposing the sacrificial polymer and allowing the byproducts to diffuse through the encapsulating dielectric. The diffusivity of the polymer decomposition products is adequate at elevated temperatures to allow the formation of an air-gap. The decomposition of a 5 μm thick polymer film results in less than 100 A of residue. Electromagnetic simulation shows that the effective dielectric constant of silicon dioxide (e = 4.2) can be lowered to 2.4-2.8 for relevant structures.

Fabrication of microchannels using polynorbornene photosensitive sacrificial materials

© 2003 The Electrochemical Society, Inc. All rights reserved. Except as provided under U.S. copyright law, this work may not be reproduced, resold, distributed, or modified without the express permission of The Electrochemical Society (ECS).

Protecting groups for 193-nm photoresists

Two versions of 193-nm single layer resists based on acrylic polymer chemistry have been described previously. The version 1 resist is a tool-testing version and is based on a methacrylate terpolymer structure. Its etch resistance analogue (version 2 resist) contains alicyclic compounds attached to the acrylic backbone. Key to enabling the performance of version 2 resist are the use of steroid additives which behave principally as thermomechanical modifiers to improve the mechanical properties of these rigid polymers through plasticization. We used the tertiary-butyl ester protecting group in these resists for thermal stability and other considerations. This paper describes an investigation of the impact of acid-cleavable protecting group structure on the properties of a series of model acrylic polymers. In this investigation, factors such as thermochemical stability, reactivity to photogenerated acid, and dissolution properties of exposed films as a function of dose were examined. A new highly reactive protecting group is introduced in this study, the tetrahydrofuranyl ester (THF) of methacrylic acid. Additionally, we introduce a new polymer family (polynorbornenes) with superior etch resistance, significantly broadening the polymer chemistry available for the construction of new 193-nm photoresists.

Lithographic Characteristics and Thermal Processing of Photosensitive Sacrificial Materials

Previously, a novel method for fabricating microfluidic and microelectromechanical devices with buried microchannel structures using thermally sacrificial polymers was reported. These previous methods required separate lithographic and etching sequences to pattern the sacrificial polymer. In this work, a more advanced approach in which the sacrificial material is radiation sensitive and can be patterned directly using standard lithographic techniques is explored. The lithographic performance of a new class of photosensitive polynorbornene (PNB) sacrificial materials has been characterized. The effect of soft bake and postexposure bake (PEB) on the cross-linking of photodefinable PNB has also been investigated. It was found that significant cross-linking of PNB occurs after exposure during the subsequent postexposure bake. However, this phenomenon is strongly dependent on the soft bake conditions used in preparing the sample, presumably due to varying levels of residual solvent content. This may he due to the high mass transport of the reactive species because of evaporation of residual solvent and shrinking of polymer matrix during the PEB profess. No noticeable influence of residual solvent on cross-linking has been found during exposure.

High-performance polymeric materials for waveguide applications

The ever-increasing need for economical, reliable, and high- performance optical interconnects for telecommunication and data communication markets demands new innovative solutions. Polymer technology being developed at BFGoodrich is focused on satisfying this demand. It is based on proprietary polynorbornene polymers that exhibit excellent optical, thermal and mechanical properties essential for fabrication of reliable components for integrated optics. Typical polymer waveguide systems exhibit a tradeoff between thermal and optical performance. The uniqueness of the polynorbornene system is that these tradeoffs are minimized. The intrinsic properties of the polynorbornene system include low transmission loss (<0.1 dB/cm at 820 nm), wide spectral range (<0.4 dB/cm at 450 nm and <0.1 dB/cm at 515-870nm), low birefringence ((Delta) n(in plane)<10-5, (Delta) n(out of plane) <10-3 at 820 nm, consistent difference in index over a wide temperature range, long-term thermal stability (>2000 hours at 125 degree(s)C), high glass transition temperature (>280 degree(s)C), and low moisture absorption (<0.1%). The combination of these characteristics offers advantages over existing plastic materials for visible and near IR applications such as those used in the datacom market. Candidate materials have been identified as core and cladding components for optical waveguides. The refractive index of a typical core material is 1.53, and of a typical clad material, 1.50 at 820 nm. The difference in index between core and cladding is approximately 0.03 over a broad range of wavelength (515-870nm). Preliminary results indicate that the difference in index between core and cladding tracks with temperature, which is in line with out expectation since these polymers have similar structures at the molecular level. Fabrication of functional waveguides has been demonstrated using a conventional cast and cure process at the lab scale. Optical performance of the constituent materials and the waveguide devices will be discussed in the paper.

Polynorbornene for Low K Interconnection

Within the microelectronics industry, there is an ongoing trend toward miniaturization coupled with higher performance. The scaling of transitors toward smaller dimensions, higher speeds, and lower power has resulted in an urgent need for low dielectric constant interlevel insulators. Low dielectric constant interlevel dielectrics have already been identified as being critical to the realization of high performance integrated circuits in the SLA Roadmap. Thus, there exists a need in the microelectronics industry for a thermally stable, noncorrosive low dielectric constant polymer with good solvent resistance, high glass transition temperature, good mechanical performance and good adhesive properties, particularly to copper. In addition, the desired dielectric material should be capable of being processed in environmentally friendly solvents, and the final thermal and electrical performance should not be affected by manufacturing or post environmental conditions. High glass transition temperature polynorbornenes are being developed which provide many of these desired features. This polymer family is produced via a new transition metal catalyzed polymerization. Attributes which make polynorbornene particularly attractive in microelectronics include: (i) excellent thermal performance, (ii) adhesion to conductors without the use of adhesion promoters or barrier layers, (iii) very low moisture absorption (

Design of an etch-resistant cyclic olefin photoresist

In the quest for a high performance 193 nm photoresist with robust plasma etching resistance equivalent to or better than the DUV resists of today, we have focused on the use of cyclic olefin polymers. In this paper, we will discuss monomer synthesis, polymerization approaches, polymer properties and early lithographic results of 193 nm photoresists formulated from cyclic olefin polymeric materials made from a metal-catalyzed addition polymerization process. The goal of this work is to produce a 193 nm photoresist with excellent imaging performance and etch resistance exceeding DUV resists, and in fact approaching novolak-based photoresists.